Linear polyamino and/or polyammonium polysiloxane copolymers II

ABSTRACT

The invention relates to linear polyamino- and/or polyammonium-polysiloxane copolymers, particularly hydrophilic polyquaternary polysiloxane copolymers, and to their use in cosmetic formulations, in laundry detergents or for surface-treating substrates.

The invention relates to linear polyamino- and/orpolyammonium-polysiloxane copolymers, particularly hydrophilicpolyquaternary polysiloxane copolymers, and to their use as wash-stablehydrophilic softeners.

Polysiloxanes containing amino groups are known for use as textilesofteners (EP 441530). The introduction as side chains of aminostructures modified by ethylene oxide/propylene oxide units produces animprovement in the effect (U.S. Pat. Nos. 5,591,880, 5,650,529). Thealkylene oxide units here allow controlled adjustment of thehydrophilic/hydrophobic balance. Disadvantages are, from the syntheticstandpoint, the difficulty of the esterification that is included in thesynthesis strategy, namely that of amino alcohols with siloxane-bondedcarboxylic acid groups, and, in respect of the softening properties, thegeneral comb structure of the products.

To eliminate these disadvantages proposals have been made to reactα,ω-epoxy-modified siloxanes with α,ω-amino-functionalized alkyleneoxides, and to use these products as hydrophilic softeners (U.S. Pat.Nos. 5,807,956, 5,981,681).

In order to improve the substantivity, experiments have been undertakenon introducing quaternary ammonium groups into alkylene oxide-modifiedsiloxanes.

Branched, alkylene oxide-modified polysiloxane quats (“polysiloxanequats” are polydiorganosiloxane-polyalkylammonium compounds) have beensynthesized from α,ω-OH-terminated polysiloxanes and trialkoxysilanes bycondensation. The quaternary ammonium structure is introduced via thesilane, with the quaternary nitrogen atom being substituted by alkyleneoxide units (U.S. Pat. No. 5,602,224).

Strictly comblike alkylene oxide-modified polysiloxanequats havelikewise been described (U.S. Pat. No. 5,098,979). The hydroxyl groupsof polyethersiloxanes with comblike substitution are converted withepichlorohydrin into the corresponding chlorohydrin derivatives. That isfollowed by quaternization with tertiary amines. For this reason thehydroxyl groups of polyethersiloxanes with comblike substitution havealternatively been esterified with chloroacetic acid. The carbonylactivation allows the final quaternization to be completed more easily(U.S. Pat. Nos. 5,153,294, 5,166,297).

U.S. Pat. No. 6,242,554 describes α,ω-difunctional siloxane derivativeswhich each possess a separate quaternary ammonium and alkylene oxideunit. These materials are distinguished by an enhanced compatibilitywith polar environments.

The reaction of α,ω-diepoxides with tertiary amines in the presence ofacids yields α,ω-diquaternary siloxanes, which can be used for haircarepurposes (German Patent Specification 37 19 086). Besidestetraalkyl-substituted quaternary ammonium structures, aromaticimidazolinium derivatives as well are claimed.

Reducing the ease with which the compounds are washed out of hair can beachieved by reacting the α,ω-diepoxides with ditertiary amines in thepresence of acids to give long-chain polyquaternary polysiloxanes (EP282720). Aromtic quaternary ammonium structures are not disclosed.Derivatives of this kind are addressed in U.S. Pat. No. 6,240,929. In afirst step, for this purpose, diamines having two imidazole units aresynthesized from imidazole and suitable difunctional alkylating agents,and these diamines are subsequently converted, in a manner analogous tothat of EP 282720, into polyquaternary polysiloxanes. Cationic compoundsprepared in this way are said to possess a further-increasedcompatibility with the anionic surfactants that are present in cosmeticformulations.

Nevertheless, the stability with respect to being washed out of hairrelates to the short-term attack of, principally, water and very mild,non-skin-irritant surfactants, whereas wash-stable hydrophilic softenersfor textiles have to resist the attack of concentrated surfactantsolutions possessing high fat and soil solvency. A further complicatingfactor is that modern laundry detergents contain strongly alkalinecomplexing agents, oxidative bleaches, and complex enzyme systems, andthe fibers are exposed to their effects often for hours at elevatedtemperatures.

WO 02/10259 discloses polyquaternary polysiloxane compounds incorporatedin which additionally are hydrophilic units (EO units), and in which thearrangement and sequence of the quat units to hydrophilic units can bemodified such that it is subsequently possible to achieve a betterhydrophilic soft hand without loss of substantivity on, for example,textiles (cotton, polyester).

Further approaches at improving the compatibility with anionicsurfactant systems and/or the efficiency of siloxane deposition onsurfaces are directed at the use of relatively large amounts of cationicsurfactants (WO 00/71806 and WO 00/71807) or at the utilization ofcationic polysaccharide derivatives (J. V. Gruber et al., Colloids andSurfaces B: Biointerfaces 19 (2000) 127-135) in mixtures withpolydimethylsiloxanes.

Highly charged, very hydrophilic synthetic polycationics are likewisecapable of improving the compatibility with anionic surfactant systems(U.S. Pat. No. 6,211,139), or of associating with fibers in the presenceof solutions of anionic surfactants (WO 99/14300). Among the compoundsdescribed in the latter publication are polyimidazolinium derivatives.

None of the proposals addressed constitutes a satisfactory solution tothe problem of obtaining the silicone-mediated soft hand and thepronounced hydrophilicity following original finishing of a textilematerial even when said material is subject to the attack of aggressivedetergent formulations in the course of repeated laundering operationsat normal or elevated temperature.

A fundamentally different approach is described in DE-A 32 36,466. Thereaction of OH-terminated siloxanes with alkoxy silanes containingquaternary ammonium structures yields reactive intermediates which aresaid to crosslink with suitable crosslinking agents, such astrialkoxysilanes, on the fiber surface to form wash-stable layers. Adecisive disadvantage of this approach is that the hours-long stabilityrequired of an aqueous finishing bath cannot be guaranteed and thatunforeseen crosslinking reactions may occur in the bath even beforetextile finishing.

WO 02/10257 discloses polysiloxane compounds containing quaternaryammonium groups and synthesized from diamines, diepoxides containingpolydiorganosiloxane groups, and di(haloalkyl) ester polyethercompounds. As an inevitable result of their preparation, however, thesepolysiloxane compounds include a certain fraction of ester groups, whichspecifically are sensitive to hydrolysis under alkaline conditions, as akey constituent. Moreover, in the polysiloxane compounds describedtherein, the ratio between softening polydiorganosiloxane blocks andhydrophilic blocks is rigid. The properties of these polysiloxanecompounds cannot, therefore, always be tailored to particularrequirements. for instance, for certain applications, the hydrophilicityof these polysiloxane compounds is not always satisfactory, while inother applications the soft hand or the substantivity leaves somethingto be desired.

None of the solutions cited teaches how it is possible to achieve afurther increase in hydrophilicity and substantivity while retaining thesoft hand, or how, in particular, these properties can, so to speak, betailored for specific applications.

It is therefore an object of the invention to provide linearpolysiloxane copolymers, their preparation, and their use as wash-stablehydrophilic softeners, the linear polysiloxane copolymers endowing thetextiles after corresponding application with a soft hand typical forsilicones and with a pronounced hydrophilicity, with this pattern ofproperties not being lost even after exposure to detergent formulationsin the course of repeated laundering operations at normal or elevatedtemperature. It is a further object of the invention to provide for theuse of these linear polysiloxane copolymers as separate softeners afterthe laundering of fibers and/or textiles, and as softeners in launderingwith formulations based on nonionic or on anionic/nonionic surfactants.Additionally the linear polysiloxane copolymers ought to prevent orreduce textile creasing. A final object of the present invention is toprovide a linear polysiloxane copolymer whose properties in respect ofsoft hand, substantivity, hydrophilicity or the like can be easilytailored to a respective application.

The present invention accordingly provides linear polyamino- andpolyammonium-polysiloxane copolymers containing the repeating unit-[Q-V-]-  (I)in which Q is selected from the group consisting of

-   -   —NR—,    -   —N⁺R₂—,    -   a saturated or unsaturated diamino-functional heterocycle of the        formulae

-   -   an aromatic diaminofunctional heterocycle of the formula

-   -   a trivalent radical of the formula:

-   -   a trivalent radical of the formula

-   -   in which R in each case is hydrogen or a monovalent organic        radical,    -   Q not bonding to a carbonyl carbon atom,    -   V represents at least one group V¹ and at least one group V²    -   in which    -   V² is selected from divalent or trivalent, straight-chain,        cyclic or branched, saturated, unsaturated or aromatic        hydrocarbon radicals having up to 1000 carbon atoms (not        including the carbon atoms of the polysiloxane radical Z²,        defined below) and containing, if desired, one or more groups        selected from        -   —O—, —CONH—,        -   —CONR²—, in which R² is hydrogen, a monovalent,            straight-chain, cyclic or branched, saturated, unsaturated            or aromatic hydrocarbon radical having up to 100 carbon            atoms, which may contain one or more groups selected from            —O—, —NH—, —C(O)— and —C(S)—, and which may if desired be            substituted by one or more substituents selected from the            group consisting of a hydroxyl group, an unsubstituted or            substituted heterocyclic group preferably containing one or            more nitrogen atoms, amino, alkylamino, dialkylamino,            ammonium, polyether radicals and polyetherester radicals,            and, if there are two or more groups —CONR²—, they may be            identical or different,        -   —C(O)— and —C(S)—, and    -   the radical V² may if desired by substituted by one or more        hydroxyl groups, and    -   the radical V² contains at least one group -Z²- of the formula

-   -   in which    -   R¹ can be identical or different and is selected from the group        consisting of C₁ to C₂₂ alkyl, fluoro(C₁-C₁₀)alkyl and C₆-C₁₀        aryl, and n₁=20 to 1000,    -   V¹ is selected from dihydric or trihydric, straight-chain,        cyclic or branched, saturated, unsaturated or aromatic        hydrocarbon radicals having up to 1000 carbon atoms, which if        desired may contain one or more groups selected from        -   —O—, —CONH—,        -   —CONR²—, in which R² is as defined above, it being possible            for the groups R² in the groups V¹ and V² to be identical or            different,        -   —C(O)—, —C(S)— and -Z¹-, in which -Z¹- is a group of the            formula

-   -   -   in which        -   R¹ is as defined above, it being possible for the groups R¹            in the groups V¹ and V² to be identical or different, and        -   n₂=0 to 19,        -   and the radical V¹ may if desired be substituted by one or            more hydroxyl groups,

    -   with the provisos

    -   that the radical V¹ may not contain any ester group(s) —C(O)—O—        and/or —O—C(O)—,

    -   that the trivalent radicals Q and the trivalent radicals V¹ or        V² serve exclusively for saturating one another within the        linear main chain of the stated polysiloxane copolymers, and

    -   that in the stated polysiloxane copolymer the molar ratio        V²/V¹≠1,

    -   and in which the positive charges resulting from the ammonium        groups are neutralized by organic or inorganic acid anions,

    -   and the acid addition salts thereof.

In one preferred embodiment of the invention Q is selected from thegroup consisting of

—NR—,

—N⁺R²—,

a saturated or unsaturated diamino-functional heterocycle of theformulae

an aromatic diamino-functional heterocycle of the formula

in which R is as defined above, and V¹ and V² are divalent radicals.

In one preferred embodiment of the invention Q is selected from thegroup consisting of

an amino unit of the formula

an ammonium unit of the formula

a quaternized imidazole unit of the structure

a quaternized pyrazole unit of the structure

a diquaternized piperazine unit of the structure

a monoquaternized piperazine unit of the structure

a monoquaternized piperazine unit of the structure

a diquaternized unit of the structure

a monoquaternized unit of the structure

a monoquaternized unit of the structure

a diquaternized unit of the structure

a monoquaternized unit of the structure

a monoquaternized unit of the structure

in which

-   t is from 2 to 10,-   R² is as defined above, and the definition of R² may be identical to    or different from the definition of the above group R²,-   R³ has the definition of R², it being possible for R² and R³ to be    identical or different, or-   R² and R³ together with the positively charged nitrogen atom form a    five- to seven-membered heterocycle, which if desired may    additionally contain one or more nitrogen, oxygen and/or sulfur    atoms,-   R⁵, R⁶ and R⁷ can be identical or different and are selected from    the group consisting of H, halogen, hydroxyl group, nitro group,    cyano group, thiol group, carboxyl group, alkyl group,    monohydroxyalkyl group, polyhydroxyalkyl group, thioalkyl group,    cyanoalkyl group, alkoxy group, acyl group, acetyloxy group,    cycloalkyl group, aryl group, alkylaryl group, and groups of the    type —NHR^(W), in which R^(W) is H, alkyl group, monohydroxyalkyl    group, polyhydroxyalkyl group, acetyl group or ureido group, and    pairs of adjacent radicals R⁵, R⁶ and R⁷ may, with the carbon atoms    bonding them to the heterocycle, form aromatic five- to    seven-membered rings, and-   R⁸ has the definition of R², it being possible for R⁸ and R² to be    identical or different.

In a further preferred embodiment of the present invention V² is a groupof the formula-V²*-Z²-V²*-in which Z² is as defined above and V²* is a divalent straight-chaincyclic or branched, saturated, unsaturated or aromatic hydrocarbonradical having up to 40 carbon atoms, which if desired may contain oneor more groups selected from —O—, —CONH—, —CONR²—, in which R² is asdefined above, —C(O)— and —C(S)—, and the radical V²* may if desired besubstituted by one or more hydroxyl groups.

Preferably also V² and/or V²* contains no ester groupings —C(O)—O—and/or —O—C(O)—.

Where Q is a trivalent radical of the formula

these radicals do not serve for the branching of the polysiloxanecopolymers; instead, these radicals are joined exclusively to trivalentradicals V¹ or V², forming cyclic structures which are a constituent ofthe linear main chain, such as, for example, a structural element of theformula

Likewise the trivalent radicals V¹ and/or V² do not serve for thebranching of the linear polysiloxane copolymers.

In the abovementioned embodiment the linear polysiloxane copolymer ofthe invention contains the following repeating units:-[V²*-Z²-V²*-Q]- and -[V¹-Q]-.

The molar ratio of the repeating units -[V²*-Z²-V²*-Q]- to -[V¹-Q]-corresponds to the ratio V²/V¹≠1.

On the basis of these molar ratios the linear polysiloxane copolymers ofthe invention necessarily include blocks which contain more than one-[V¹-Q]- unit and/or -[V²-Q]- unit linked to one another.

As elucidated in greater depth below in connection with the process ofthe invention for preparing the linear polysiloxane copolymers of theinvention, the blocklike sequences which contain more than one -[V¹-Q]-unit linked to one another, and thus in which V²/V¹ is <1, are joined,depending on mode of preparation, regularly to the V²-Q- units orirregularly to the V²-Q- units.

The meaning of this is as follows:

in the case of regular joining, where, for example, a prepolymercorresponding to the group -Q-[V¹-Q]_(x)- is reacted with monomer unitscorresponding to V² in a molar ratio of 1:1, the linear polysiloxanecopolymers may be represented as follows:-{V²-Q-[V¹-Q]_(x)-}-.x here may preferably be 1.01 to 2000 and is the average value. Thelinear polysiloxane copolymers represented with the formula-{V²-Q-[V¹-Q]_(x)-}- are characterized in that they containsubstantially no interlinked -V²-Q- units, or, in other words, two-V²-Q- units are always interrupted by at least one -V¹-Q- unit.

If V²/V¹ is >1, then x in the above formula is preferably approximately0.001 to 0.99. In this case the linear polysiloxane copolymers containat least one interlinked -V²-Q- unit, or, in other words, two V¹-Q-units are always interrupted by at least one V²-Q- unit.

In the case of the irregular joining, in which, for example, monomerscorresponding to Q units are reacted with monomer units corresponding toV¹ and monomer units corresponding to V² in a ratio Q/(V¹+V²), whereV²/V¹≠1, of 1:1, the linear polysiloxane copolymers may be representedas follows:-Q-(V¹,V²)-,in which the ratio V²/V¹≠1. In this case the groups V¹ and V² aredistributed randomly over the copolymer chain. In contradistinction tothe linear polysiloxane copolymers prepared by the regular joining, thiscopolymer may also contain adjacent -Q-V²- and/or -Q-V¹- units.

In a further preferred embodiment of the present invention the group V¹is selected from divalent, straight-chain, cyclic or branched,saturated, unsaturated or aromatic hydrocarbon radicals having up to 400carbon atoms, which may if desired contain one or more groups selectedfrom —O—, —CONH—, —CONR²—, in which R² is as defined above, —C(O)—,—C(S)— and -Z¹-, in which -Z¹- is a group of the formula

in which

-   R¹ is C₁ to C₃ alkyl, fluoro(C₃-C₆)alkyl or C₆ aryl, and n₂ is as    defined above.

In a further preferred embodiment of the present invention the group Qis selected from:

a quaternized imidazole unit of the structure

a quaternized pyrazole unit of the structure

a diquaternized piperazine unit of the structure

a monoquaternized piperazine unit of the structure

a monoquaternized piperazine unit of the structure

a monoquaternized unit of the structure

in which R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are as defined above.

In a further preferred embodiment of the present invention, particularlyin applications where increased hydrophilicity of the linearpolysiloxane copolymers of the invention is a priority, the molar ratioV²/V¹ complies with the relationshipV²/V¹<1,more preferably with the relationship0.0005<V²/V¹<0.9,more preferably still with the relationship0.005<V²/V¹<0.8,more preferably still with the relationship0.01<V²/V¹<0.5.

In a further preferred embodiment of the present invention, especiallyin applications where an increased soft hand with consistentsubstantivity of the linear polysiloxane copolymers of the invention isa priority, such as in the case of certain textile finishes, forexample, the molar ratio V²/V¹ preferably complies with the relationshipV²/V¹>1,more preferably with the relationship1<V²/V¹<1000,more preferably still with the relationship1.1<V²/V¹<100,more preferably still with the relationship2<V²/V¹<20.With preference:

-   R¹=C₁ to C₁₈ alkyl, especially methyl, ethyl,    perfluoroalkylethylene, such as trifluoropropyl, and phenyl,-   n₁=20 to 400, more preferably 20 to 300, especially 20 to 200. In a    further preferred embodiment n₁ is between 20 and 50 or between 80    and 200. The number n₁ is the average degree of polymerization of    the diorganosiloxy units in the group Z².-   n₂=0 to 15, more preferably 0 to 10, especially 0 to 5, more    especially 0. The number n₂ is the average degree of polymerization    from Mn of the diorganosiloxy units in the group Z¹.-   V²*=a divalent straight-chain, cyclic or branched, saturated,    unsaturated C₃ to C₁₆ hydrocarbon radical or aromatic C₈ to C₂₀    hydrocarbon radical which if desired may contain one or more groups    selected from —O—, —CONH—, —CONR²—, —C(O)— and —C(S)— and may be    substituted by one or more than one OH group, in which-   R²=hydrogen, a monovalent straight-chain, cyclic or branched,    saturated, unsaturated C₁ to C₁₆ hydrocarbon radical or aromatic C₆    to C₁₆ hydrocarbon radical which may contain one or more groups    selected from —O—, —NH—, —C(O)— and —C(S)— and which may if desired    be substituted by one or more than one hydroxyl group, and, if there    are two or more groups —NR², they may be identical or different,

a quaternized imidazole unit of the structure

a diquaternized piperazine unit of the structure

a monoquaternized piperazine unit of the structure

a monoquaternized piperazine unit of the structure

a monoquaternized unit of the structure

in which R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are as defined above.With particular preference

-   V²* is a divalent straight-chain, cyclic or branched, saturated,    unsaturated or aromatic hydrocarbon radical having up to 16 carbon    atoms, which may contain one or more groups selected from —O—,    —CONH—, —CONR²—, in which R² is as defined above, —C(O)— and —C(S)—,    and may be substituted by one or more hydroxyl groups. More    preferably still -V²*- is selected from groups of the following    formulae:

R² is preferably:

-   hydrogen, —CH₃, —CH₂CH₃, —(CH₂)₂CH₃, —(CH₂)₃CH₃, —(CH₂)₅CH₃,    —CH₂CH₂OH,

with

-   R⁴=straight-chain, cyclic or branched C₁ to C₁₈ hydrocarbon radical    which may contain by one or more groups selected from —O—, —NH—,    —C(O)—, and —C(S)— and may be substituted by one or more OH groups,    especially unsubstituted C₅ to C₁₇ hydrocarbon radicals which are    derived from the corresponding fatty acids or else hydroxylated C₃    to C₁₇ radicals which can be traced back to hydroxylated carboxylic    acids, especially saccharide carboxylic acids, and are very    especially

Furthermore, R² is preferably:

in which t and R⁵ to R⁸ are as defined above,

in which t and R⁵ to R⁷ are as defined above, and

in which t and R², R³ and R⁸ are as defined above.V¹ is preferably

-   -   —R⁹—, in which R⁹ is a divalent, saturated or mono- or        polyunsaturated, straight-chain or branched hydrocarbon radical        having two to 25 carbon atoms,    -   —(CH₂)_(u)—R¹⁰—(CH₂)_(u)—, in which R¹⁰ is an aromatic group,    -   —[CH₂CH₂O]_(q)—[CH₂CH(CH₃)O]_(r)—CH₂CH₂—,    -   —CH(CH₃)CH₂O[CH₂CH₂O]_(q)—[CH₂CH(CH₃)O]_(r)—CH₂CH(CH₃)—    -   —CH₂CH(OH)CH₂—,    -   —CH₂CH(OH)(CH₂)₂CH(OH)CH₂—,    -   —CH₂CH(OH)CH₂OCH₂CH(OH)CH₂OCH₂CH(OH)CH₂— and    -   —CH₂CH(OH)CH₂O—[CH₂CH₂O]_(q)—[CH₂CH(CH₃)O]_(r)—CH₂CH(OH)CH₂—        in which

-   u is from 1 to 3,

-   q and r are from 0 to 200, preferably from 0 to 100, more preferably    from 0 to 70, and with particular preference 0 to 40, and

-   q+r>0.    Preferred variants of V¹ are

-   alkylene, alkenylene, alkynylene and aryl units, especially those of    the structures

-   —[CH₂]_(o)—    where o=2 to 6,

polyalkylene oxide units, especially those of the structures

-   —[CH₂CH₂O]_(q)—[CH₂CH(CH₃)O]_(r)—CH₂CH₂—,-   —CH(CH₃)CH₂O[CH₂CH₂O]_(q)—[CH₂CH(CH₃)O]_(r)—CH₂CH(CH₃)—    with-   mono-, di- or polyhydroxy-functional units, especially those of the    structures-   —CH₂CH(OH)CH₂—, —CH₂CH(OH)(CH₂)₂CH(OH)CH₂—,-   —CH₂CH(OH)CH₂OCH₂CH(OH)CH₂OCH₂CH(OH)CH₂—,-   —CH₂CH(OH)CH₂O—[CH₂CH₂O]_(q)[CH₂CH(CH₃)O]_(r)—CH₂CH(OH)CH₂—    with-   q=0 to 200,-   r=0 to 200    Preferably q=1 to 50, in particular 2 to 50, especially 1 to 20,    very especially 1 to 10, and also 1 or 2, r=0 to 100, in particular    0 to 50, especially 0 to 20, very especially 0 to 10, and also 0 or    1 or 2.

The invention further provides a process for preparing the linearpolysiloxanes of the invention, in which

-   -   a) at least one amine compound selected from a diamine compound        and/or a primary or secondary monoamine compound is reacted with        at least two difunctional organic compounds capable of reacting        with the amino functions of the amine compound, the molar ratio        of the organic compounds being chosen so as to meet the        condition V²/V¹≠1,    -   b) at least two moles of an amine compound selected from a        diamine compound and/or a primary or secondary monoamine        compound are reacted with one mole of a difunctional organic        compound capable of reacting with the amino functions of the        amine compound, to form a diamine compound (monomer), which is        subsequently reacted with at least one amine compound selected        from a diamine compound and/or a primary or secondary monoamine        compound and with at least one further difunctional organic        compound capable of reacting with the amino functions of the        amine compounds,    -   c) an amine compound selected from a diamine compound and/or a        primary or secondary monoamine compound is reacted with a        difunctional organic compound capable of reacting with the amino        functions of the amine compounds, to form a diamine compound        (amino-terminated oligomer), which is subsequently reacted with        at least one difunctional organic compound capable of reacting        with the amino functions of the diamine compounds,    -   d) an amine compound selected from a diamine compound and/or a        primary or secondary monoamine compound is reacted with a        difunctional organic compound capable of reacting with the amino        functions of the amine compound, to form a difunctional compound        capable of reacting with amino functions (difunctional        oligomer), which is subsequently reacted with at least one amine        compound selected from a diamine compound and/or a primary or        secondary monoamine compound and with at least one further        compound capable of reacting with amino functions,        it being possible if desired to add monofunctional, preferably        tertiary, monoamines or suitable monoamines not capable of chain        propagation, and/or monofunctional compounds capable of reacting        with amino functions, as chain terminators, and the        stoichiometry of the amino functions and the functional groups        capable of reacting with amino functions always being        approximately 1:1 in the last stage of the reaction,        and it being possible for any amino functions present to be        protonated, alkylated or quaternized.

Variant a), in which at least one diamine compound selected from adiamine compound and/or primary or secondary monoamine compound isreacted with at least two difunctional organic compounds capable ofreacting with the amino functions of the amine compound, the molar ratioof the organic compounds being chosen so as to meet the conditionV²/V¹≠1, can accordingly be depicted schematically, for example, asfollows:-[N-N]-+-[V¹]-+-[V²]-→-[Q-(V¹,V²)]- or-[N]-+-[V¹]-+-[V²]-→-[Q-(V¹,V²)]-where -[N-N]- can include a cyclic diamine corresponding to thedefinition of Q or a V¹-containing diamine -[N-V¹-N]- or a V²-containingdiamine -[N-V²-N]-, such as, in particular, -[N-V²*-Z²-V²*-N]-, thelatter giving rise in each case to two Q units and/or one V¹ and/or twoV² units, where -[V¹]- and -[V²] are intended to denote monomerscorresponding to the repeating units V¹ and V²,and -[N]- denotes a primary or secondary monoamine suitable for chainpropagation.

In this case at least one higher polyalkylated amine unit or quaternaryammonium unit Q is formed from the -[N-N]- and/or -[N]- units, it beingpossible for the secondary or tertiary amino functions formed during thepolymerization to be protonated or quaternized in a separate step afterthe polymerization where appropriate. Preference is given to theformation of quaternary ammonium units.

Preferred examples of -[N-N]- are as described in more detail below:piperazine and imidazole; preferred diamine units -[N-V¹-N]- include,for example: polymethylenediamines, such astetramethyl-hexamethylenediamine, α,ω-diamino-terminated polyethers,such as Jeffamines, for example, etc.

Preferred diamine units -[N-V²*-Z²-V²*-N]- include, for example,reaction products of α,ω-dihydropolydialkylsiloxanes with allylamines.

Preferred examples of -[N]- are as described in more detail below, e.g.,dimethylamine.

The use of diamines -[N-N]- is preferred per se.

Preferred -[V¹]- monomers include, for example, epichlorohydrin,bisepoxides or bisacrylates. It is also possible with preference toreact mixtures of the stated -[V¹]- monomers, such as mixtures ofepichlorohydrin, bis-chloroalkyl esters or bisepoxides, for example.

Preferred -[V²]- monomers and monomers of formula -[V²*-Z²-V²*]-, inwhich Z² is as defined above and -[V²*] represents a functionalizedgroup corresponding to the repeating unit V²*. Preferred -[V²]- monomersfor forming the V² repeating units are, in particular,α,ω-diepoxy-terminated polydialkylsiloxanes.

Variant b) can be carried out both with diamines, -[N-N]-, and withsuitable monoamines -[N]-, and can be represented diagrammatically, forexample, as follows:

Variant b1)

-   Step 1): 2-[N-N]-+-[V²]- or -[V¹]-→-[N-N-V¹-N-N]- or -[N-N-V²-N-N]--   Step 2.1): -[N-N-V²-N-N]-+-[V¹]-+-[N-N]-→,-   Step 2.2): -[N-N-V¹-N-N]-+-[V²]-+-[N-N]-→,    the stoichiometry being chosen so as to meet the condition    V²/V¹<1:3.

With respect to the monomer units -[N-N]-, -[V¹]- and -[V²]- used withpreference, the remarks made with respect to step a) apply.

Variant b2)

-   Step 1): 2-[N]-+-[V²]- or -[V¹]-→-[N-V¹-N]- or -[N-V²-N]--   Step 2.1): -[N-V²-N]-+-[V¹]-+-[N]-→,-   Step 2.2): -[N-V¹-N]-+-[V²]-+-[N]-→,    it being possible to carry out this variant, as mentioned above,    only with primary or secondary monoamines, and where with respect to    the monomer units -[N]-, -[V¹]- and -[V²]- used with preference, the    remarks made with respect to step a) apply.

Variant c) can be depicted diagrammatically, for example, as follows:

Variant c1)

-   Step 1): -[N-N]-+-[V¹]-→-[N-N-(V¹-N-N)_(x)]--   Step 2): -[N-N-(V¹-N-N)_(x)]-+-[V²]-→    where with respect to the monomer units -[N-N]-, -[V¹]- and -[V²]-    used with preference, the remarks made with respect to step a)    apply.    Variant c2)-   Step 1): -[N]-+-[V¹]-→-[N-(V¹-N)_(x)]--   Step 2): -[N-(V¹-N)_(x)]-+-[V²]-→    where with respect to the monomer units -[N]-, -[V¹]- and [V²]- used    with preference, the remarks made with respect to step a) apply.

Variant d) can be depicted diagrammatically, for example, as follows:

Variant d1)

-   Step 1): -[V¹]-+-[N-N]-→-[V¹-(N-N-V¹)_(x)]--   Step 2): -[V¹-(N-N-V¹)_(x)]-+-[V²]-+-[N]- or -[N-N]-→    where with respect to the monomer units -[N-N]-, -[V¹]- and [V²]-    used with preference, the remarks made with respect to step a)    apply.    Variant d2)-   Step 1): -[V¹]-+-[N]-→-[V¹-(N-V¹)_(x)]--   Step 2): -[V¹-(N-V¹)_(x)]-+-[V²]-+-[N]- or -[N-N]-→    where with respect to the monomer units -[N]-, -[V¹]- and -[V²]-    used with preference, the remarks made with respect to step a)    apply.

For all of the variants depicted diagrammatically above it is the casethat it is also possible to use mixtures of monoamines -[N]- anddiamines -[N-N]-.

With particular preference the functional groups of the difunctionalcompounds capable of reacting with amino functions are selected from thegroup consisting of epoxy groups and haloalkyl groups.

A preferred starting point for the syntheses of the linear polysiloxanecopolymers of the invention are α,ω Si—H functionalized siloxanes of thegeneral structure

where R¹ is as defined above and n, in accordance with the desiredrepeating unit, V¹ or V², is n₂ or n₁, which are defined as above. Wherethey are not available commercially, these siloxanes can be prepared byknown methods, e.g., by equilibration (Silicones, Chemie undTechnologie, Vulkan-Verlag, Essen 1989, pp. 82-4).

The initial introduction of the structural elements V²* and Q can takeplace, for example, in two ways.

On the one hand it is possible first to attach unsaturated structurescarrying tertiary amino functions, such as N,N-dimethylallylamine, forexample, directly to the siloxane in α,ω position by hydrosilylation.This operation is general knowledge. (B. Marciniec, ComprehensiveHandbook on Hydrosilylation, Pergamon Press, Oxford 1992, pp. 122-4).

On the other hand it is preferred first, by hydrosilylation, to generatereactive α,ω-functionalized intermediates, which can subsequently beconverted into α,ω-ditertiary amino structures or, directly, into thequaternary ammonium structures of the invention. Suitable startingmaterials for generating reactive intermediates are, for example,halogenated alkenes or alkynes, especially allyl chloride, allylbromide, chloropropyne and chlorobutyne, unsaturated halocarboxylicesters, especially allyl chloroacetate, propargyl chloroacetate, allyl3-chloropropionate and propargyl 3-chloropropionate, andepoxy-functional alkenes, such as vinylcyclohexene oxide and allylglycidyl ether, for example. The general procedure of hydrosilylationswith representatives of the aforementioned groups of substance islikewise known (B. Marciniec, Comprehensive Handbook on Hydrosilylation,Pergamon Press, Oxford 1992, pp. 116-21, 127-30, 134-7, 151-5).

In a subsequent step the reactive intermediates can then be reacted withcompounds which carry secondary amino functions. Suitablerepresentatives are N,N-dialkyl-amines, examples being dimethylamine,diethylamine, dibutylamine, diethanolamnine and N-methylglucamine,cyclic secondary amines, examples being morpholine and piperidine, aminoamides which carry secondary amino functions, examples being thereaction products of diethylenetriamine or dipropylenetriamine withlactones, such as γ-butyrolactone, glucono-δ-lactone andglucopyranosylarabolactone (DE-A 4318536, examples 11a, 12a, 13a), orsecondary-tertiary diamines, such as N-methylpiperazine, for example. Itis especially preferred to utilize corresponding imidazole derivativesor pyrazole derivatives, especially imidazole and pyrazole, forintroducing tertiary amino functions.

Particularly suitable partners for the epoxide derivatives used withpreference in one embodiment are the stated secondary-tertiary diamines,and also imidazole and pyrazole. In this way the alkylations can bedirected regioselectively and without additional effort at the nitrogenatoms which carry hydrogen atoms.

In order to ensure quantitative conversion of the reactive moieties intotertiary amino structures, the amines are used in a ratio of

-   1≦Σ secondary amino groups: reactive groups≦10, preferably 1 to 3,    especially 1 to 2, very especially 1. Any amine excesses must be    removed.

The attachment of the above-described α,ω-ditertiary aminosiloxanes tomonomer units -[V¹]- corresponding to V¹, or to a prepolymer unit-[V¹-(Q-V¹)_(x)]-, leads to the formation of higher polyalkylated amineunits and/or quaternary ammonium units, and can again take place in twoadvantageous ways.

On the one hand it is preferred separately to produce a stronglyhydrophilic, polyquaternary, difunctional precondensate-[V¹-(Q-V¹)_(x)]-, which at a suitable point in time is united with theα,ω-ditertiary aminosiloxanes and reacts to give the polyquaternarysiloxane copolymer.

The preparation of highly charged difunctional prepolymers differing inchain length -[V¹-(Q-V¹)_(x)]- is described by way of example in WO99/14300 (examples 1 to 7, table 11). In dependence on the molar ratioof V¹ and the parent amine of Q it is possible to produce either aprepolymer terminated by amino groups or a prepolymer terminated byother reactive groups (e.g., epoxy and/or haloalkyl groups).

For the case of the attachment of a prepolymer terminated by aminogroups -[N-(V¹-N)_(x)]- to the amine function of an α,ω-ditertiaryaminosiloxanes structure it is possible, for example, to use analkylating and/or quaternizing difunctional monomer -[V¹]-,corresponding to the repeating unit V¹ and selected, for example, frombisepoxides, epichlorohydin and bishaloalkyl compounds. In this contextthere is no need to mention that different groups V¹ may result in theprepolymer and in the connecting link between prepolymer andα,ω-ditertiary aminosiloxane structure.

For the case of a prepolymer terminated by reactive groups, such as-[V¹-(Q-V¹)_(x)]-, a direct attachment to the amine function of theα,ω-ditertiary aminosiloxane structure may take place without furtherlinkers, since an excess of the component that produces V¹ has alreadybeen used during prepolymer synthesis.

As an alternative to the separate preparation of a precondensate-[V¹-(Q-V¹)_(x)]-, highly charged blocks can be built up in parallel forincorporation into the copolymer. This means that the α,ω-ditertiaryaminosiloxane is introduced and reacted together with the startingcomponents for the construction of -[V¹-(Q-V¹)_(x)]-, i.e., for example,-[V¹]- and mono- and diamines of the abovementioned definition -[N]-and/or -[N-N-]-.

Finally it is possible for the α,ω-ditertiary aminosiloxane withlong-chain siloxane unit Z² or short-chain siloxane unit Z¹, and/or theα,ω-difunctional siloxane -[V²*-Z²-V²*]- or -[V¹]-, to be metered instages over a period of time into the initial charge of the componentsfor constructing -[V¹-(Q-V¹)_(x)]-, or else, conversely, for thesecomponents to be added in stages to the α,ω-ditertiary aminosiloxaneand/or α,ω-difunctional siloxane.

The preliminary preparation of prepolymers terminated by amino groups,such as -[N-(V¹-N)_(x)]-, for example, opens up the possibility ofperforming the copolymer formation directly with suitable reactiveintermediates, such as epoxy derivatives, for example.

It is likewise preferred to include the reactive intermediates and thestarting components for the construction of -[V¹-(Q-V¹)_(x)]- togetherin the initial charge and then to bring them to reaction,

finally it is possible to meter the reactive intermediates into theinitial charge of the components for constructing -[V¹-(Q-V¹)_(x)]- instages over a period of time or else, conversely, to add thesecomponents in stages to the reactive intermediate.

Irrespective of the choice of one of the above-described reactionpathways, and of the closely related question of whether amino unitsfirst terminate the siloxane or else terminate the prepolymer, theoverall stoichiometry is chosen such that the sum of the amino functionsto the groups reactive with them amounts to approximately 1:1.

In the context of the invention it is possible to deviate from thispreferred overall stoichiometry. In that case, however, products areobtained which no longer have the envisaged length of the highlycharged, hydrophilic block -[V¹-(Q-V¹)_(x)]- and which additionallyleave behind an excess of an unreacted starting component.

As well as the above-treated overall stoichiometry of the reaction, thechoice of the component(s) forming the repeating unit V¹ is of greatimportance for the pattern of properties of the products.

The introduction of alkylene, alkenylene, alkynylene and aryl unitstakes place preferably starting from the corresponding halides,especially chlorides and bromides. Exemplary representatives are1,6-dichlorohexane, 1,4-dichlorobut(2-)ene, 1,4-dichlorobut(2-)yne and1,4-bis(chloromethyl)benzene.

Polyalkylene oxide units may likewise be introduced by the α,ω-dihalogencompounds. They are obtainable from the oligomeric and polymericalkylene oxides of the general compositionHO[CH₂CH₂O]_(q)—[CH₂CH(CH₃)O]_(r)Hwhere q and r are as defined above, by, for example, chlorinating thehydroxyl groups with SOCl₂ (Organikum, Organisch-chemischesGrundpraktikum, 17th edition, VEB Deutscher Verlag der Wissenschaften,Berlin 1988, pp. 189-90). Mono-, di- or polyhydroxy-functional units asgroup V¹ can be introduced starting from epoxide derivatives.

Commercial examples are 1-chloro-2,3-epoxypropane, glycerol1,3-bisglycidyl ether and diethylene glycol diglycidyl ether andneopentyl glycol diglycidyl ether.

Where not available commercially, the desired diepoxides can besynthesized, for example, by reacting the corresponding diols with1-chloro-2,3-epoxypropane under alkaline conditions.

It is within the bounds of the invention to introduce siloxane chains Z¹into the structure of V¹. This gives rise to the possibility, amongothers, of using siloxane chains of different length to construct theoverall molecule. A preferred variant is to incorporate into V¹ siloxanechains Z¹ of the chain-length range n₂=0 to 19, preferably 0 to 15, morepreferably 0 to 10, especially 0 to 5, more especially 0. Examples ofsuitable starting materials for the incorporation are the correspondingα,ω-diepoxides.

In the case of the reaction of epoxides with primary or secondary aminesit should be borne in mind that for alkylations of tertiary amino groupsit is necessary to add one mole of H+ per mole of epoxide/tertiaryamine.

The choice of suitable amines as starting components for the formationof Q in the repeating unit -[V¹-(Q-V¹)_(x)]- likewise determines to ahigh degree the molecular structure. The use of ditertiary amines(corresponding to -[N-N]-), for example,N,N,N′,N′-tetramethylethylenediamine,N,N,N′,N′-tetramethyltetramethylenediamine,N,N,N′,N′-tetramethylhexamethylenediamine and N,N′-dimethylpiperazine,leads to products in which each nitrogen atom of the repeating unit isquaternized.

The use of secondary-tertiary diamines, such as N-methylpiperazine, forexample, opens up a pathway to repeating units -[V¹-(Q-V¹)_(x)]-, inwhich tertiary and quaternary amine and ammonium structures,respectively, are present in the ratio of 1:1. Partial or completesubsequent quaternization of remaining tertiary amino structuresconstitutes one preferred variant for setting a desired high density ofquaternary ammonium groups. The corresponding aromatic amines imidazoleand pyrazole, respectively, lead to products having a delocalizedcharge.

When primary-tertiary diamines are used, N,N-dimethylpropylenediamineand 1-(3-aminopropyl)imidazole, for example, especially in combinationwith diepoxides, it is possible to construct comblike structures, forwhich the degree of quaternization during a final alkylation isselectable. In principle it is also possible for the alkylations to beset to degrees of quaternization of, on average; less than onequaternary ammonium group per repeating unit -[V¹-(Q-V¹)_(x)]-. It is,however, preferred to quaternize at least one nitrogen atom perrepeating unit.

Starting from disecondary amines, such as piperazine,N,N′-bis(2-hydroxyethyl)-hexamethylenediamine andN,N′-bis(2-hydroxypropyl)hexamethylenediamine, for example, it is inprinciple also possible to synthesize repeating units -[V¹-(Q-V¹)_(x)]-having an average content of less than one quaternary ammonium group. Inthis case the disecondary amines first yield polytertiarilyamino-modified siloxane copolymers or else prepolymers, which in a finalreaction can be fully or partly quaternized to -[V¹-(Q-V¹)_(x)]-. Inthis variant as well, however, it is preferred to quaternize at leastone nitrogen atom per repeating unit.

Suitable quaternizing agents include the groups of substance that aregeneral knowledge, such as alkyl halides, halocarboxylic esters, epoxidederivatives in the presence of H⁺, and dialkyl sulfates, especiallydimethyl sulfate.

The preparation of disecondary amines that are not availablecommercially takes place in one preferred embodiment starting from thecorresponding diprimary amines, such as hexamethylenediamine, forexample, by alkylation with epoxides, such as ethylene oxide, propyleneoxide or isopropyl glycidyl ether, for example, utilizing the differentreaction rates of primary and secondary amines.

It has already been established that within the bounds of the inventionthe possibility exists of introducing siloxane chains Z¹ into thestructure of V¹. Suitable starting materials designated were, by way ofexample, the reactive intermediates α,ω-diepoxides.

Suitable neutralizing anions A⁻ for the positive charges that resultfrom the ammonium groups include preferably the ions that are formedduring the quaternization, such as halide ions, especially chloride andbromide, alkyl sulfates, especially methosulfate, carboxylates,especially acetate, propionate, octanoate, decanoate, dodecanoate,tetradecanoate, hexadecanoate, octadecanoate and oleate, and sulfonates,especially toluenesulfonate. By means of ion exchange, however, it isalso possible to introduce other anions. Examples that may be mentionedinclude organic anions, such as polyethercarboxylates andpolyethersulfates.

The quaternization reactions are performed preferably in water, polarorganic solvents or mixtures of both stated components. Suitability ispossessed for example by alcohols, especially methanol, ethanol,isopropanol and n-butanol, glycols, such as ethylene glycol, diethyleneglycol, triethylene glycol, the methyl, ethyl and butyl ethers of saidglycols, 1,2-propylene glycol and 1,3-propylene glycol, ketones, such asacetone and methyl ethyl ketone, esters, such as ethyl acetate, butylacetate and 2-ethylhexyl acetate, ethers, such as tetrahydrofuran andnitro compounds, such as nitromethane. The choice of solvent is governedessentially by the solubility of the reactants, by the target reactiontemperature and by the presence of any reactivity that disrupts thereaction.

The reactions are performed in the range from 20° C. to 130° C.,preferably 40° C. to 100° C.

In order to avoid the formation of gel-like linear polyorganosiloxanepolymers that are not fully soluble, it is advantageous to place anupper limit on the molar weight. A limit on the molecular weight isplaced by means of the end stopping that arises during the reactionbetween epoxides and any alcohol or water that may be present in thereaction system, or, alternatively, through the additional use oftertiary amines, such as trialkylamines or monofunctional amino-reactivecompounds.

In other words, the linear polyorganosiloxane polymers may contain notonly the terminal groups that result naturally from the reaction of themonomeric starting materials but also from monofunctional chainterminators, such as trialkylamines, etc., and, for example, resultantammonium, amino, ether or hydroxyl end groups.

The present invention further provides for the use of the linearpolyorganosiloxane polymers of the invention and, respectively, of thelinear polyorganosiloxane polymers obtained by the process of theinvention in cosmetic formulations, in laundry detergents or forsurface-treating substrates.

The linear polyorganosiloxane polymers of the invention, which combinethe softening properties of siloxane structures with the tendency ofquaternary ammonium groups toward adsorption on negatively chargedsurfaces of solids can be used with success in cosmetic formulations forskincare and haircare, in polishes for treating and finishing hardsurfaces, in formulations for drying automobiles and other hard surfacesafter machine washing, for finishing textiles, textile fibers, paper,paper fibers, paper webs, including the pretreatment and finishtreatment of fiber, textile and paper, finishing paper for the cosmeticsand sanitary segments, especially permanent hydrophilic softeners, asseparate softeners after the laundering of textiles withanionic/nonionic detergent formulations, as softeners in textile laundryformulations based on anionic/nonionic surfactants, and also as anironing aid and as agents for preventing or reducing textile creasing.The invention further provides compositions comprising at least one ofthe linear polyorganosiloxane polymers of the invention together with atleast one further ingredient usual for the composition, such as cosmeticcompositions, laundry detergent compositions, polishes, shampoos,ironing aids and crease-free finishes.

Use of the polysiloxane derivatives of the invention in hair cosmetologyapplications leads to favorable effects in terms of gloss, fixing(hold), body, volume, moisture regulation, color retention,environmental protection (UV, salt water, etc.), reshapeability,antistatic properties, colorability, combability, etc. In other words,the quaternary polysiloxane compounds can be used with preference in thecosmetics and haircare formulas of WO 02-10257.

EXAMPLES Example 1

19.38 g (0.225 mol of amino groups) ofN,N,N′,N′-tetramethylhexanediamine and 12.14 g (0.202 mol) of aceticacid are mixed with 30 ml of deionized water at room temperature. Addeddropwise to this solution over the course of 15 minutes are 35.26 g(0.202 mol of epoxy groups) of a 50% strength solution of ethyleneglycol diglycidyl ether in ethylene glycol dimethyl ether. Thetemperature climbs to 92° C. Within an afterreaction time of 20 minutesa gel-like mass develops. This gel mass is added to a mixture of 150 g(0.025 mol of epoxy groups) of an epoxysiloxane of the structure

0.75 g (0.0125) of acetic acid, 2.5 g (0.0125 mol) of dodecanoic acid,0.33 g (0.0025 mol; 45% strength aqueous solution) of trimethylamine and50 ml of 2-propanol. Reaction takes place over 16 hours at 90° C.Subsequently all of the volatile constituents are stripped off at 20hPa/80° C. This gives 182 g of a white, solid to waxlike material. Thefollowing formula shows the quantitative composition:

The ratio V²/V¹ for this example is about 0.058.

Example 2

27.6 g (0.255 mol of epoxy groups) neopentyl diglycidyl ether and 54.8 g(0.0316 mol of epoxy groups) of a siloxane of the structure

are dissolved at room temperature in 200 ml of 2-propanol. Added to thissolution are 17.8 g (0.142 mol of primary amino groups) of1-(3-aminopropyl)imidazole. The ring-opening reaction takes place at 80°C. for 8 hours. Subsequently 17.9 g (0.142 mol) of dimethyl sulfate areadded and the quaternization reaction is carried out over the course of5 hours. Residues of dimethyl sulfate are destroyed by adding 10 ml ofwater. After all of the constituents which boil at up to 20 hPa/60° C.have been stripped off, 97.5 g of a brown, turbid product are obtained.The following formula shows the quantitative composition:

The ratio V²/V¹ in this example is about 0.12.

Example 3

9.67 g (0.112 mol of amino groups) N,N,N′,N′-tetramethylhexanediamine,0.17 g (0.0013 mol) of 45% strength aqueous trimethylamine solution,11.35 g (0.056 mol) of dodecanoic acid and 3.4 g (0.056 mol) of aceticacid are mixed with 6 ml of deionized water and 124 g of 2-propanol atroom temperature and the mixture is heated to 50° C. Introduced dropwiseinto the clear solution are 86.85 g (0.0124 mol of epoxy groups) of anepoxysiloxane of the structure

and 18.28 g (0.101 mol of epoxy groups) of an epoxysiloxane of thestructure

The reaction mixture is heated to 84° C. and maintained at thistemperature for 14.5 hours. After 15 minutes, incipient turbidificationwas observed. After the end of the reaction the mixture is divided. Fromone half of the mixture all of the volatile constituents are strippedoff at 20 hPa/80° C. This gives 54 g of a viscous, almost white mass.From the other half of the mixture the volatile constituents are removedat 20 hPa/25° C. This gives 58 g of a pale yellowish, viscous oil. Thefollowing formula shows the quantitative composition:

The ratio V²/V¹ in this example is about 0.058.

1. Linear polyammonium-polysiloxane copolymers containing the repeatingunit-[Q-V-]-  (I) in which Q is selected from the group consisting of

a quaternized imidazole unit of the structure

a quaternized pyrazole unit of the structure

a diquaternized piperazine unit of the structure

a monoquaternized piperazine unit of the structure

a monoquaternized piperazine unit of the structure

a monoquaternized unit of the structure

in which R² is a monovalent, straight-chain, cyclic or branched,saturated, unsaturated or aromatic hydrocarbon radical having up to 100carbon atoms, which may contain one or more groups selected from —O—,—NH—, —C(O)— and —C(S)—, and which may if desired be substituted by oneor more substituents selected from the group consisting of a hydroxylgroup, an unsubstituted or substituted heterocyclic group preferablycontaining one or more nitrogen atoms, amino, alkylamino, dialkylamino,ammonium, polyether radicals and polyetherester radicals, and, if thereare two or more groups —CONR²—, they may be identical or different, R₃has the definition of R², it being possible for R² and R³ to beidentical or different, or R² and R³ together with the positivelycharged nitrogen atom form a five- to seven-membered heterocycle, whichif desired may additionally contain one or more nitrogen, oxygen and/orsulfur atoms, R⁵, R⁶ and R⁷ can be identical or different and areselected from the group consisting of hydrogen, halogen, hydroxyl group,nitro group, cyano group, thiol group, carboxyl group, alkyl group,monohydroxyalkyl group, polyhydroxyalkyl group, thioalkyl group,cyanoalkyl group, alkoxy group, acyl group, acetyloxy group, cycloalkylgroup, aryl group, alkylaryl group, and groups of the type —NHR^(W), inwhich R^(W) is hydrogen, alkyl group, monohydroxyalkyl group,polyhydroxyalkyl group, acetyl group or ureido group, and pairs ofadjacent radicals R⁵, R⁶ and R⁷ may, with the carbon atoms bonding themto the heterocycle, form aromatic five- to seven-membered rings, and R⁸has the definition of R², it being possible for R⁸ and R² to beidentical or different, Q not bonding to a carbonyl carbon atom, Vrepresents at least one group V¹ or at least one group V² in which V² isselected from divalent or trivalent, straight-chain, cyclic or branched,saturated, unsaturated or aromatic hydrocarbon radicals having up to1000 carbon atoms (not including the carbon atoms of the polysiloxaneradical Z², defined below) and containing, if desired, one or moregroups selected from —O—, —CONH—, —CONR²—, in which R² is as definedabove, —C(O)— and —C(S)—, and the radical V² may if desired bysubstituted by one or more hydroxyl groups, and the radical V² containsat least one group -Z²- of the formula

in which R¹ can be identical or different and is selected from the groupconsisting of C₁ to C₂₂ alkyl, fluoro(C₁-C₁₀)alkyl and C₆-C₁₀ aryl, andn₁=20 to 1000, V¹ is selected from divalent or trivalent,straight-chain, cyclic or branched, saturated, unsaturated or aromatichydrocarbon radicals having up to 1000 carbon atoms, which if desiredmay contain one or more groups selected from —O—, —CONH—, —CONR²—, inwhich R² is as defined above, it being possible for the groups R² in thegroups V¹ and V² to be identical or different, —C(O)—, —C(S)— and -Z¹-,in which -Z¹- is a group of the formula

in which R¹ is as defined above, it being possible for the groups R¹ inthe groups V¹ and V² to be identical or different, and n₂=0 to 19, andthe radical V¹ may if desired be substituted by one or more hydroxylgroups, with the provisos that the radical V¹ may not contain any estergroup(s) —C(O)—O— and/or —O—C(O)—, and that in the stated polysiloxanecopolymer the molar ratioV²/V¹≠1, and in which the positive charges resulting from the ammoniumgroups are neutralized by organic or inorganic acid anions, and the acidaddition salts thereof.
 2. Linear polyammonium-polysiloxane copolymersaccording to claim 1, in which V²is a group of the formula-V²*-Z²-V²*- in which Z² is as defined above and V²* is a divalentstraight-chain cyclic or branched, saturated, unsaturated or aromatichydrocarbon radical having up to 40 carbon atoms, which if desired maycontain one or more groups selected from —O—, —CONH—, —CONR²—, in whichR² is as defined above, —C(O)— and —C(S)—, and the radical V²* may ifdesired be substituted by one or more hydroxyl groups.
 3. Linearpolyammonium-polysiloxane copolymers according to claim 1, in which thegroup V¹ is selected from divalent, straight-chain, cyclic or branched,saturated, unsaturated or aromatic hydrocarbon radicals having up to 600carbon atoms, which may if desired contain one or more groups selectedfrom —O—, —CONH—, —CONR²—, in which R² is as defined above, —C(O)—,—C(S)— and -Z¹-, in which -Z¹- is a group of the formula

in which R¹ is C₁ to C₃ alkyl, fluoro(C₃-C₆)alkyl or C₆ aryl, and n₂ isas defined above.
 4. Linear polyammonium-polysiloxane copolymersaccording to claim 1, in which the molar ratio V²/V¹ complies with therelationshipV²/V¹<1.
 5. Linear polyammonium-polysiloxane copolymers according toclaim 1, in which the molar ratio V²/V¹ complies with the relationship0.0005<V²/V¹<0.9.
 6. A process for preparing the linearpolyammonium-polysiloxane copolymers according to claim 1, in which a)at least one amine compound selected from a diamine compound and/or aprimary or secondary monoamine compound is reacted with at least twodifunctional organic compounds capable of reacting with the aminofunctions of the amine compound, the molar ratio of the organiccompounds being chosen so as to meet the condition V²/V¹≠1, b) at leasttwo moles of an amine compound selected from a diamine compound and/or aprimary or secondary monoamine compound are reacted with one mole of adifunctional organic compound capable of reacting with the aminofunctions of the amine compound, to form a diamine compound (monomer),which is subsequently reacted with at least one amine compound selectedfrom a diamine compound and/or a primary or secondary monoamine compoundand with at least one further difunctional organic compound capable ofreacting with the amino functions of the amine compounds, c) an aminecompound selected from a diamine compound and/or a primary or secondarymonoamine compound is reacted with a difunctional organic compoundcapable of reacting with the amino functions of the amine compounds, toform a diamine compound (amino-terminated oligomer), which issubsequently reacted with at least one difunctional organic compoundcapable of reacting with the amino functions of the diamine compounds,or d) an amine compound selected from a diamine compound and/or aprimary or secondary monoamine compound is reacted with a difunctionalorganic compound capable of reacting with the amino functions of theamine compound, to form a difunctional compound capable of reacting withamino functions (difunctional oligomer), which is subsequently reactedwith at least one amine compound selected from a diamine compound and/ora primary or secondary monoamine compound and with at least one furthercompound capable of reacting with amino functions, it being possible ifdesired to add monofunctional, preferably tertiary, monoamines orsuitable monoamines not capable of chain propagation, and/ormonofunctional compounds capable of reacting with amino functions, aschain terminators, and the stoichiometry of the amino functions and thefunctional groups capable of reacting with amino functions always beingapproximately 1:1 in the last stage of the reaction, and it beingpossible for any amino functions present to be protonated, alkylated orquaternized.
 7. The process according to claim 6, in which thefunctional groups of the difunctional compounds capable of reacting withamino functions are selected from the group consisting of epoxy groupsand haloalkyl groups.
 8. A process of applying a cosmetic comprisingapplying a composition including the linear polyammonium-polysiloxanecopolymers according to claim
 1. 9. A process of treating fibers orfinishing fibers comprising applying the formulation according to claim1 to fibers.
 10. Compositions comprising at least one linearpolyammonium-polysiloxane copolymer according to claim 1, together withat least one further ingredient customary for the composition.
 11. Alaundry detergent composition comprising the composition according toclaim
 10. 12. A process of washing laundry comprising applying thelinear polyammonium-polysiloxane copolymer according to claim 1 tolaundry.
 13. A process of surface treating a substrate comprisingapplying the polyammonium-polysiloxane compound of claim 1 to thesubstrate.
 14. A cosmetic composition comprising the compositionaccording to claim 10.